On the structure, stress and optical properties of CVD tungsten oxide films

Tungsten oxide thin films were prepared by low temperature chemical vapor deposition (CVD) process from a metallorganic precursor at atmospheric pressure. The influence of the deposition temperature and oxygen flow-rate on the film structure, density and built-in stress were investigated in a comparative way employing different characterization techniques. The XRD structural analysis of the films showed co-existence of WO₃ and WO_2.9 phases. On the basis of the performed studies it was inferred that the film density decreases, the film stresses change and the film transmission increases at higher oxygen flow-rate values during the deposition. The growth window for preparation of tungsten oxide films with very low density, facilitating fast kinetics of the electrochromic effect, was established.     

Facile synthesis of antimony-doped tin oxide nanoparticles by a polymer-pyrolysis method

In this article, antimony-doped tin oxide (ATO) nanoparticles was synthesized by a facile polymer-pyrolysis method. The pyrolysis behaviors of the polymer precursors prepared via in situ polymerization of metal salts and acrylic acid were analyzed by simultaneous thermogravimetric and differential scanning calorimetry (TG-DSC). The structural and morphological characteristics of the products were studied by powder X-ray diffraction (XRD) and transmission electron microscope (TEM). The results reveal that the ATO nanoparticles calcined at 600 °C show good crystallinity with the cassiterite structure and cubic-spherical like morphology. The average particle size of ATO decreases from 200 to 15 nm as the Sb doping content increases from 5 mol% to 15 mol%. Electrical resistivity measurement shows that the resistivity for the 10-13 mol% Sb-doped SnO₂ nanoparticles is reduced by more than three orders compared with the pure SnO₂ nanoparticles. In addition, due to its versatility this polymer-pyrolysis method can be extended to facile synthesis of other doped n-type semiconductor, such as In, Ga, Al doped ZnO, Sn doped In₂O₃.     

Nonstoichiometric orthorhombic titanium oxide, TiO2−δ and its thermochromic properties

Redox relationship among anatase, rutile, and a new nonstoichiometric orthorhombic titanium oxide was elucidated. Single crystal of nonstoichiometric orthorhombic titanium oxide TiO_1.94 was prepared by reducing a single crystal of rutile TiO₂ at 950 °C in H₂ for 1 h based on this relationship. The single crystallinity was demonstrated by both the Laue and the Debye-Scherrer methods. Temperature dependence of the conductivity and the reflectance spectrum was measured for the single crystal of TiO_1.94, and it was found that the reflectivity in near-infrared region over 1700 nm gradually increased with increasing temperature. “Smart windows” using this titanium oxide was proposed.     

In situ etching WO3 nanoplates: Hydrothermal synthesis, photoluminescence and gas sensor properties

A novel hydrothermal process using p-nitrobenzoic acid as structure-directing agent has been employed to synthesize plate-shaped WO₃ nanostructures containing holes. The p-nitrobenzoic acid plays a critical role in the synthesis of such novel WO₃ nanoplates. The morphology, structure and optical property of the WO₃ nanoplates have been characterized by transmission electron microcopy (TEM), scanning electron microcopy (SEM), X-ray diffraction (XRD) and photoluminescence (PL). The lateral size of the nanoplates is 500-1000 nm, and the thickness is about 80 nm. The formation mechanism of WO₃ nanoplates is discussed briefly. The gas sensitivity of WO₃ nanoplates was studied to ethanol and acetone at different operation temperatures and concentrations. Furthermore, the WO₃ nanoplate-based gas sensor exhibits high sensitivity for ethanol and acetone as well as quick response and recovery time at low temperature.     

High temperature thermopower and electrical resistivity studies in the transparent conducting oxide Sn doped MgIn2O4

Sn doping in an n-type transparent conducting oxide MgIn₂O₄ is carried out and its effect on the high temperature transport properties viz. thermopower and electrical resistivity is studied. A solid solution exists in the composition window Mg_1+xIn_2−2xSn_xO₄ for 0 < x ≤ 0.4. The band gap as well as the transport properties increases with increasing Sn concentration. The high temperature resistivity properties indicate degenerate semiconducting behavior for all the compositions. The highest figure of merit obtained is 0.12 × 10⁻⁴ K⁻¹ for the parent compound at 600 K.     

Characterization and enhanced field emission properties of carbon nanotube bundle arrays coated with N-doped nanocrystalline anatase TiO2

Anatase TiO₂ nanocrystals (NCs) were deposited onto patterned carbon nanotube (CNT) bundle arrays to form a TiO₂/CNT composite using metal organic chemical vapor deposition (MOCVD) using titanium-tetraisopropoxide (Ti(OC₃H₇)₄) as a source reagent. The N-doped TiO₂/CNT composite was then fabricated using nitrogen plasma treatment. The structural and spectroscopic properties of TiO₂/CNT composites were characterized by field-emission scanning electron microscopy, micro-Raman spectroscopy and X-ray photoelectron spectroscopy. The combined geometrical structure and low electron affinity effects of N-doped TiO₂ led to a low turn-on field of 1.0 V μm⁻¹ at a current density of 10 μA cm⁻², a low threshold field of 1.9 V μm⁻¹ at a current density of 1 mA cm⁻², a high field enhancement factor of 3.0 × 10³, and long-term stability for the N-doped TiO₂/CNT composite. The results revealed that the N-doped TiO₂/CNT composite can be a potential candidate for field emission devices.     

The effect of annealing on structural, electrical and optical properties of nanostructured ITO films prepared by e-beam evaporation

Tin doped indium oxide (ITO) thin films with composition of 9.42 wt% SnO₂ and 89.75 wt% In₂O_3, and impurities balanced on glass substrates at room temperature have been prepared by electron beam evaporation technique and then were annealed in air at different temperatures from 350 to 550 °C for 1 h. XRD pattern showed that increasing annealing temperature increased the crystallinity of thin films and at 550 °C high quality crystalline thin films with grain size of about 37 nm were obtained. Conductivity of ITO thin films was increased by increasing annealing temperature and conductivity obtained results in 350-550 °C temperature range were also excellently fitted in both Arrhenius-type and Davis-Mott variable-range hopping conductivity models. The UV-vis transmittance spectra were also confirmed that the annealing temperature has significant effect on the transparency of thin films. The highest transparency over the visible wavelength region of spectrum (93%) obtained at 550 °C on annealing temperature. It should be noted that this thin film was deposited on substrate at room temperature. This result obtained is equivalent with those values that have already been reported but with high-level (20 wt%) tin doped indium oxide thin films and also at 350 °C substrate temperature. The allowed direct band gap at the temperature range 350-550 °C was estimated to be in the range 3.85-3.97 eV. Band gap widening with an increase in annealing temperature was observed and is explained on the basis of Burstein-Moss shift. A comparison between the electron beam evaporation and other deposition techniques showed that the better figure of merit value can be obtained by the former technique. At the end we have compared our results with other techniques.     

The tetragonal-orthorhombic transition and the associated changes in the properties of Pr0.5−xNdxSr0.5MnO3

The transition from the tetragonal (I4/mcm) to the orthorhombic (Imma) structure associated with a change in A- to CE-type antiferromagnetism in the Pr_0.5−xNd_xSr_0.5MnO₃ has been investigated by X-ray diffraction as well as magnetization and resistivity measurements. The transition is found to occur between x=0.1 and 0.2.     

Electrical properties of thick-film NTC thermistor composed of Ni0.8Co0.2Mn2O4 ceramic: Effect of inorganic oxide binder

The thick-film NTC thermistors were prepared by screen printing Ni_0.8Co_0.2Mn₂O₄ ceramic on the alumina. The influence of inorganic oxide binder composition and thickness of thermistor layer on the thermistor constant and initial resistivity are studied. The relation between the resistivity (ρ) and the absolute temperature for the prepared thick-film thermistor comply with Arrhenius equation. The room temperature sheet resistivities of the thick films were in the range 0.56-7.45 MΩ cm and temperature sensitivity index in the range 1492-3335 K. Binder composition dependent agglomeration of microcrystallites is observed in the microstructure of the thick-film Ni_0.8Co_0.2Mn₂O₄ ceramic. The spinel ceramic was prepared by oxalate co-precipitation and sintering.     

Low temperature synthesis of porous copper/zinc oxide

A two-step urea aqueous solution process at a low temperature (90 °C) was employed for the preparation of a copper/zinc oxide material. Well defined porous spherical particles with average sizes of around 5 μm in diameter were prepared first and then used as a support for further copper-zinc precipitation. It was found that the particle composition and shape were changed with applied stirring speed (100 rpm or 200 rpm) and that particle size is inversely proportional to the copper content in the particles. The particles preserved their size and shape after the heat treatment. Prepared Cu/ZnO samples showed catalytic activity for the reaction of steam reforming of methane. Samples were characterized by scanning field emission electron microscopy, energy dispersive X-ray analyses, X-ray powder diffraction, surface area analyses, and atomic absorption spectroscopy.     

Preparation and characterization of indium zinc oxide thin films by electron beam evaporation technique

In this work, the preparation of In₂O₃-ZnO thin films by electron beam evaporation technique on glass substrates is reported. Optical and electrical properties of these films were investigated. The effect of dopant amount and annealing temperature on the optical and electrical properties of In₂O₃-ZnO thin films was also studied. Different amount of ZnO was used as dopant and the films were annealed at different temperature. The results showed that the most crystalline, transparent and uniform films with lowest resistivity were obtained using 25 wt% of ZnO annealed at 500 °C.     

Synthesis and optical properties of hierarchical pure ZnO nanostructures

We report the catalyst-free synthesis of hierarchical pure ZnO nanostructures with 6-fold structural symmetry by two-step thermal evaporation process. At the first step, the hexagonal-shaped nanowires consisting of a great deal of Zn and little oxide were prepared via the layer-by-layer growth mechanism; and at the second step, hierarchical pure ZnO nanostructures were synthesized by evaporating the Zn source on the basis of the step-one made substrate. Scanning electron microscopy, transmission electron microscope images, and the corresponding selected area electron diffraction pattern have been utilized to reveal the screw dislocation growth mechanism, through which the single crystal ZnO nanorods are epitaxially grown from the side-wall of central axial nanowires. Raman and photoluminescence spectra further indicate that, for the hierarchical ZnO nanostructures, the ultraviolet peak is related to the free exciton recombination, while the oxygen vacancies and high surface-to-volume ratio are responsible for the strong green peak emission.     

Synthesis and electrical properties of ordered perovskite oxide Cd3−x−yCuxAyTeO6 (A = Li, Na; 0.00 ≤ x, y ≤ 0.15)

Polycrystalline Cd_3−x−yCu_xA_yTeO₆ (A = Li, Na) samples were prepared by solid-state reaction, and their crystal structure and electrical properties were investigated. In Cd_3−xCu_xTeO₆ and Cd_3−yA_yTeO₆ (A = Li, Na), the maxim solubility of x and y was 0.15 and 0.15 for A = Li, 0.05 for A = Na, respectively. For co-substituted samples Cd_2.9−yCu_0.1Li_yTeO₆ and Cd_2.9−yCu_0.1Na_yTeO₆, the maxim solubility of x was the same as single substitution above-mentioned. The alkali-metal substituted samples Cd_3−yA_yTeO₆ (A = Li, Na) showed a negative Seebeck coefficient, which indicates that the major conduction carriers are electron. On the other hand, the co-substituted samples Cd_2.9−yCu_0.1A_yTeO₆ (A = Li, Na) represented a positive Seebeck coefficient, and major conduction carriers were hole through substitution by copper ions.     

Preparation of hexagonal WO3 from hexagonal ammonium tungsten bronze for sensing NH3

Hexagonal tungsten oxide (h-WO₃) was prepared by annealing hexagonal ammonium tungsten bronze, (NH₄)_0.07(NH₃)_0.04(H₂O)_0.09WO_2.95. The structure, composition and morphology of h-WO₃ were studied by XRD, XPS, Raman, ¹H MAS (magic angle spinning) NMR, scanning electron microscopy (SEM), and BET-N₂ specific surface area measurement, while its thermal stability was investigated by in situ XRD. The h-WO₃ sample was built up by 50-100 nm particles, had an average specific surface area of 8.3 m²/g and was thermally stable up to 450 °C. Gas sensing tests showed that h-WO₃ was sensitive to various levels (10-50 ppm) of NH₃, with the shortest response and recovery times (1.3 and 3.8 min, respectively) to 50 ppm NH₃. To this NH₃ concentration, the sensor had significantly higher sensitivity than h-WO₃ samples prepared by wet chemical methods.     

Structural and electrical properties of Na2Pb2Eu2W2Ti4X4O30 (X = Nb, Ta) ferroelectric ceramics

A new group of tungsten bronze family Na₂Pb₂Eu₂W₂Ti₄X₄O₃₀ (X = Nb, Ta) having all the valence elements (I-VI) were prepared by a high-temperature solid-state reaction technique. The formations of the compounds were confirmed by X-ray diffraction technique with an orthorhombic structure. Surface morphology of the compounds was studied by scanning electron microscope (SEM). Studies of dielectric properties (?_r and tan δ) of the above compounds at different frequencies in a wide temperature range (300-700 K) with an impedance analyzer exhibit a ferroelectric phase transition at 580 and 394 K for Na₂Pb₂Eu₂W₂Ti₄Nb₄O₃₀ and Na₂Pb₂Eu₂W₂Ti₄Ta₄O₃₀, respectively. Ferroelectric properties of these compounds were confirmed with polarization (hysteresis) study.     

Vanadium dioxide nanobelts: Hydrothermal synthesis and magnetic properties

VO₂ (B) nanobelts were prepared by a hydrothermal method at 180 °C using V₂O₅·nH₂O sol and H₂C₂O₄·2H₂O as starting agents. The obtained nanobelts have diameters ranging from 50 to 100 nm in width, 20-30 nm in thickness with lengths up to 1.5 μm. Measurements of the static magnetic susceptibility provide evidence for two phase transitions at T₁ = 225 K and T₂ = 290 K, respectively. Below T₁, the data suggest the presence quasi-free as well as of strongly antiferromagnetic correlated spins associated to V⁴⁺-ions.     

Na substitution for La- and Mn-sites in LaMnO3 from alkali halide fluxes: low temperature synthesis, structure and properties

La_1−xNa_xMn_1−yNa_yO₃ (0.12<x<0.16; 0.04<y<0.07) have been synthesized from NaBr and NaI fluxes at relatively low temperature of 850 and 750 °C, respectively. Final composition of these oxides was obtained from chemical analysis of the elements present. The flux grown oxides crystallize in the rhombohedral structure (space group R-3c, No. 167) and are ferromagnetic metals (FMM). Chemical analysis and Rietveld refinement of X-ray data indicate Na ion is substituted for both La- and Mn-sites in the compound prepared from NaBr and NaI fluxes with 33 and 49% of Mn⁴⁺ concentration, respectively.     

Magnetic and transport properties of La0.3Ca0.7Mn0.9T0.1O3 (T = Cr, Fe, and W)

We have carried out structural, magnetic and magneto transport measurements of the electron-doped manganite La_0.3Ca_0.7MnO₃ substituted with 10% of Cr, Fe and W on the Mn site. The substitution by Cr, Fe and W suppresses the charge order transition present at 260 K in the parent compound. All the samples show a semiconducting behavior. Whereas the parent compound does not show any magneto resistance (MR) even in a field of 14 T, a maximum MR of 6% in 5 T at 25 K is observed for the Cr substituted sample that is attributed to a spin-cluster glass like states induced by Cr. The Fe and W substituted samples showed a MR of 1.5 and 3%, respectively which may be attributed to a smaller number of FM domains/spin-clusters and to an increase in anti-ferromagnetic interaction.     

Comparative study of ITO and FTO thin films grown by spray pyrolysis

Tin doped indium oxide (ITO) and fluorine doped tin oxide (FTO) thin films have been prepared by one step spray pyrolysis. Both film types grown at 400 °C present a single phase, ITO has cubic structure and preferred orientation (4 0 0) while FTO exhibits a tetragonal structure. Scanning electron micrographs showed homogeneous surfaces with average grain size around 257 and 190 nm for ITO and FTO respectively.The optical properties have been studied in several ITO and FTO samples by transmittance and reflectance measurements. The transmittance in the visible zone is higher in ITO than in FTO layers with a comparable thickness, while the reflectance in the infrared zone is higher in FTO in comparison with ITO. The best electrical resistivity values, deduced from optical measurements, were 8 × 10⁻⁴ and 6 × 10⁻⁴ Ω cm for ITO (6% of Sn) and FTO (2.5% of F) respectively. The figure of merit reached a maximum value of 2.15 × 10⁻³ Ω⁻¹ for ITO higher than 0.55 × 10⁻³ Ω⁻¹ for FTO.